Herbicidal hydantoins

ABSTRACT

Novel cycloalkane-5═-spiro-hydantoins of formula ##STR1## wherein A is selected from the group consisting of ##STR2## and the remaining substituents are defined below having strong, selective herbicidal activity and novel intermediates and a process for their preparation.

This is a continuation of application Ser. No. 157,903 filed Feb. 17, 1988, now abandoned; which is a continuation of application Ser. No. 046,622 filed May 4, 1987, now abandoned; which is a continuation of application Ser. No. 856,825, filed Apr. 28, 1986, now abandoned; which is a continuation of application Ser. No. 774,901 filed Sept. 11, 1985, now abandoned; which is a continuation of application Ser. No. 623,961, filed June 25, 1984, now abandoned; which is a continuation of application Ser. No. 492,946, filed May 9, 1983, now abandoned; which is a continuation-in-part of application Ser. No. 479,709 filed Mar. 28, 1983, now abandoned.

OBJECTS OF THE INVENTION

It is an object of the invention to provide novel hydantoins of formula I and a novel process and novel intermediates for their preparation.

It is another object of the invention to provide novel herbicidal compositions and a novel method of combatting weeds.

These and other objects and advantages of the invention will become obvious from the following detailed description.

THE INVENTION

The novel compounds of the invention are cycloalkane-5'-spiro-hydantoins for formula ##STR3## wherein A is selected from the group consisting of ##STR4## Q is selected from the group consisting of --CH-- and --N--, B is a single or multiple bridged cycloalkane of 5 to 10 carbon atoms, R₁, R₂ and R₃ are individually selected from the groups consisting of hydrogen, alkyl of 1 to 4 carbon atoms and alkenyl of 3 to 4 carbon atoms, R₄ and R₅ are individually selected from the group consisting of alkyl of 1 to 4 carbon atoms optionally substituted with alkoxy of 1 to 4 carbon atoms of alkylthio of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, cycloalkyl of 3 to 6 carbon atoms optionally substituted with alkyl of 1 to 6 carbon atoms and phenoxy, phenylthio, phenyl and benzyl optionally substituted with at least one member of the group consisting of halogen, --CF₃ and alkyl and alkoxy of 1 to 4 carbon atoms, W is oxygen and when Q is --CH--, W may be sulfur and X is selected from the group consisting of halogen, hydrogen, --CF₃ and alkyl and alkoxy of 1 to 4 carbon atoms and Y is selected from the group consisting of halogen, --CF₃ and alkyl and alkoxy of 1 to 4 carbon atoms.

Halogen in the compounds of formula I includes fluorine, chlorine, bromine and iodine with chlorine being preferred. X is preferably selected from the group consisting of hydrogen, chlorine, bromine, methyl, methoxy and trifluoromethyl. Y is preferably selected from the group consisting of chlorine, bromine, methyl, methoxy and trifluoromethyl. Preferred lower alkyl and lower alkoxy are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.butyl, tert.butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec.butoxy and tert.butoxy.

R₄ and R₅ are preferably methyl, ethyl, n-propyl, isopropyl and allyl if they are alkenyl. When R₄ and/or R₅ are phenyl or benzyl, the said groups are optionally substituted with at least one member of the group consisting of alkyl and alkoxy of 1 to 4 carbon atoms, halogen and trifluoromethyl, preferably methyl, methoxy, chlorine or bromine. The A group is preferably derived from cyclohexane, cyclopentane or homologs thereof such as menthane which may contain 1 to 3 substituents like lower alkyl such as methyl or bi- or tricyclic cycloalkanes such as carane or pinane optionally substituted with 1 to 3 lower alkyls, especially methyl.

The compounds of formula I may be prepared by a variety of known processes. The compounds of formula I wherein Q is --CH-- may be prepared by cyclizing (a) a carboxylic acid of the formula ##STR5## wherein A, W, X and Y are as defined above, in the presence of a strong inorganic acid, or (b) cyclizing an ester of the formula ##STR6## wherein A, W, X and Y are as defined above and Z is a straight-chained or branched, optionally substituted aliphatic of 1 to 20 carbon atoms or an optionally substituted araliphatic group in the presence of a base, or (c) deaminating an amino compound of the formula ##STR7## wherein A, W, X and Y are as defined above and E and E' are hydrogen or NH₂, at least one of these two groups being NH₂ to remove E and/or E'.

To prepare the compounds of formula I wherein Q is N, a spirohydantoin of the formula ##STR8## wherein A is as defined above is reacted with a pyridine of the formula ##STR9## wherein X and Y are as defined above and Z' is NO₂ or halogen with the addition of a basic compound (e.g. potassium or sodium carbonate, potassium, sodium or calcium hydroxide) at temperatures of between about 0° and about 80° C.

The cyclizing of the acid according to process (a) is conveniently effected in an aqueous or alcoholic solution in the presence of an acid such as hydrochloric acid or sulfuric acid at elevated temperature and it is easiest to heat the mixture to reflux for some time. The cyclizing of the esters according to process (b) is preferably effected in an alcohol or another organic solvent such as dioxane and the base used is preferably a tertiary organic base, e.g. triethylamine or tripropylamine. The reaction mixture is heated, generally for some hours, at reflux. In process (c) the removal of the amino group or groups is effected in a manner known per se with diazonium compounds, for example by carrying out diazotization in the presence of refluxing ethanol [Houben-Weyl, Volume 10/3 (1965), pages 116 ff] or by adding the suspension or solution of the diazonium salt to an aqueous solution of hypophosphorous acid (loc. cit., pages 131 ff) or by carrying out diazotization with alkyl nitrites in the presence of derivatives of formic acid such as dimethylformamide (loc. cit., pages 137 ff). Process (d) can be favorably influenced by the addition of a phase transfer catalyst such as a crown ether, a tetraalkylammonium salt or a tetraalkylphosphonium salt.

The compounds of the invention may, in some cases, be present in the form of cis/trans isomers and/or in enantiomeric forms and they are assigned to the cis or trans series according to the Cahn-Ingold-Prelog system. Mixtures of geometric isomers obtained according to the invention may, if desired, subsequently be resolved, e.g. by fractional crystallization, as may racemates.

If asymmetrically substituted ketones are used to prepare the starting materials of formulae VIII and X, different geometric isomers may be formed depending on the conditions of synthesis. Finally, the isomeric cycloalkane-spirohydantoins of formula I are formed accordingly therefrom [cf. for example L. Hoyer, Chem, Ber. 83, page 491 (1950)].

The starting materials III to VII are known or may be prepared analogously to known compounds by conventional methods. To prepare the compouhnds of formula III, for example, a 1-aminocycloalkanecarboxylic acid of the formula ##STR10## wherein A is as defined above is reacted with an isocyanate or isothiocyanate of the formula ##STR11## wherein W, X and Y are as defined above in aqueous or alcoholic solution at low temperatures, preferably from 0° to 10° C., in the presence of a basic substance such as sodium hydroxide solution, potassium hyroxide, solution, potassium carbonate or sodium methoxide and the compound of formula III is precipitated with a suitable acid such as hyrochloric acid, sulfuric acid or acetic acid.

The starting materials of formula IV may be obtained by reacting esters of the formula ##STR12## wherein A and Z are as defined above with an isocyanate or isothiocyanate of formula IX. The reactants IX and X are reacted in an inert solvent such as ether, methylene chloride, toluene or ethyl acetate at low temperatures, preferably 10° to 20° C. Z is generally a lower to medium alkyl of 1 to 12 carbon atoms or an optionally substituted benzyl group. The nature of the group is not normally critical provided that it does not lead to side reactions or inhibit the reaction by an unfavorable structure or reactive substituents.

The starting materials for process (c) may be obtained as follows, for example: ##STR13## wherein A and W are as defined above is reacted with a halonitrobenzene of the formula ##STR14## wherein Hal is fluorine or chlorine in the 2- or 4-position and Y is as defined above in the presence of a base such as K₂ CO₃, Na₂ CO₃, KOH, NaOH, etc. in a suitable solvent such as dimethylsulfoxide, acetonitrile or acetone, optionally with the addition of a phase transfer catalyst (crown ethers, tetraalkylammionium salts, tetraalkylphosphonium salts) at temperatures of between 0° and 150° C. to yield compounds of the formula ##STR15## wherein A, W and Y are as defined above and D and D' are H or NO₂, but at least one is NO₂.

The compounds of formula XIII are reduced to form the corresponding amino compounds of the formula ##STR16## wherein A, W and Y are as defined above and E and E' are H or NH₂ but at least one is NH₂. These amino compounds themselves or the halogenation products thereof after halogenation with, for example, Cl₂, SO₂ Cl₂, Br₂, compounds of formula V wherein X is chlorine or bromine, are then deaminated according to process (c).

The novel heribicidal compositions of the invention are comprised of a herbidically effective amount of at least one compound of formula I and an inert carrier. The compositions may be in the form of granulates, dusting agents, suspension powders, concentrates or water-dispersible granulates prepared in the usual fashion.

The compositions may be prepared by mixing or grinding the active substances of formula I with diluents or extenders such as solvents and/or solid carriers, optionally with the addition of surface-active agents such as emulsifiers or dispersants and/or stabilizing and/or anti-foaming agents and possibly other additives.

The preferred solvent is water and examples of suitable solid carriers include, for example, mineral powders such as kaolines, clays, talc, chalk, quartz, highly dispersed silicic acid, aluminum oxide and silicates. Carriers which are suitable for granulates include, on the one hand, broken and fractionated rock such as calcite, marble or pumice and granulates of organic material such as sawdust, coconut shells and corn-cobs. Suitable emulsifiers include non-ionic and anionic compounds such as polyoxyethylene-fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylarylpolyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolysates. The dispersant may be, for example, a waste sulfite liquor from wood processing or methyl cellulose, while the antifoaming agent may be a branched higher alcohol.

The concentrated preparations, which generally contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight of active substance, may optionally be made into spraying or pouring liquors by diluting them with water to give the desired concentration.

The compositions of the invention are distinguished by their powerful activity against numerous weeds, particularly monocotyledons and they are preferably applied pre-emergence. As the active compounds of formula I are well tolerated, they may be used in numerous crops such as soybeans, rice, cotton, barley, beet, potatoes, tomatoes or onions.

It is often advantageous to apply combinations of the compounds of formula I with known herbicides. Examples include combinations with urea derivatives (e.g. chlortoluron), triazine derivatives (e.g. atrazine, simazine), dinitroaniline derivatives (e.g. trifluralin), chloroacetanilide derivatives (e.g. alachlor), thiocarbamates (e.g. thiobencarb) and diphenyl ethers (e.g. acifluorfen).

The novel method of the invention for combatting weeds comprises contacting weeds with a herbicidally effective amount of at least one compound of formula I. The said compounds may be applied pre- or post-emergence and can be applied by pouring, spraying, sprinkling or dusting. Depending on the compound, the particular weed and application conditions, the usual useful amount of the active compound is 0.1 to 10 kg/ha, particularly 0.3 to 3 kg/ha.

In the following examples there are described several preferred embodiments to illustrate the invention. However, it should be understood that the invention is not intended to be limited to the specific embodiments.

EXAMPLE 1 Cyclohexane-5'-spiro-3'-(3,5-dichlorophenyl)-hydantoin

171 g (1 mol) of ethyl 1-amino-cyclohexanecarboxylate prepared by esterifying 1-amino-cyclohexanecarboxylic acid with HCl/EtOH were dissolved in 500 ml of ether and a solution of 188.5 g (1 mol) of 3,5-dichlorophenylisocyanate in 500 ml of ether was introduced over 15 minutes while cooling with ice. After all the solution had been added, the resulting mixture was stirred for 30 minutes at ambient temperature and then was vacuum filtered. The filter residue was then suspended in 500 ml of ethanol and, after the addition of 10.1 g (0.1 mol) of triethylamine, it was refluxed for 3 hours and poured into 2 liters of ice water. The precipitate formed was vacuum filtered and was washed thoroughly with water and dried in a circulating air drier to obtain 280 g (89% of theory) of the title compound melting at 210°-211° C. (from ethanol).

EXAMPLE 2 cis-2-Methylcyclohexane-5'-spiro-3'-(3,5-dichlorophenyl)-2' -thio-hydantoin

11.5 g (0.5 mol) of sodium were dissolved in 500 ml of ethanol and 79 g (0.5 mol) of cis-1-amino-2-methylcyclohexane carboxylic acid were added to the solution. Then, finely powdered 3,5-dichlorophenyl isothiocyanate was added to the resulting suspension over 30 minutes and the now clear solution was stirred for 3 hours at ambient temperature and refluxed for 3 hours. It was poured into 2 liters of ice water and the precipitate formed was vacuum filtered and washed thoroughly with water and after drying, 140 g (82% of theory) of the title compound melting at 237°-239° C. (from ethanol) were obtained. Stereochemical assignment (cis or trans) was effected in accordance with the Cahn-Ingold-Prelog system.

The starting materials of formulae III and IV for the following examples were prepared by the procedures discussed above and are reported in the following Table.

    ______________________________________                                                                                     Mp.                                No.  A                 W     X    Y    Z    [°C.]                       ______________________________________                                               ##STR17##        O     Cl   Cl   C.sub.2 H.sub.5                                                                     178- 179                           2                                                                                    ##STR18##        O     Cl   Cl   H    195- 197                           3                                                                                    ##STR19##        O     CH.sub.3                                                                            CH.sub.3                                                                            H    186- 188                           4                                                                                    ##STR20##        O     Cl   Cl   H    163- 164                           5                                                                                    ##STR21##        O     H    CF.sub.3                                                                            C.sub.2 H.sub.5                                                                     131- 132                           6                                                                                    ##STR22##        O     H    CH.sub.3                                                                            C.sub.2 H.sub.5                                                                     135- 136                           7                                                                                    ##STR23##        O     Cl   Cl   H    175- 177                           8                                                                                    ##STR24##        O     Cl   Cl   C.sub.2 H.sub.5                                                                     188- 189                           9                                                                                    ##STR25##        O     CH.sub.3                                                                            CH.sub.3                                                                            H    188- 190                           10                                                                                   ##STR26##        O     Cl   Cl   H    238- 240                           11                                                                                   ##STR27##        O     Cl   Cl   C.sub.2 H.sub.5                                                                     186- 187                           12                                                                                   ##STR28##        O     Cl   Cl   H    172- 174                           ______________________________________                                    

Using the procedure of Example 1, the following compounds of formula I described in Table I were prepared:

                  TABLE I                                                          ______________________________________                                                                                   Mp.                                  No.  A                  W     X     Y     [°C.]                         ______________________________________                                               ##STR29##         O     CH.sub.3                                                                             CH.sub.3                                                                             224- 226                             2                                                                                    ##STR30##         S     Cl    Cl    225- 227                             3                                                                                    ##STR31##         O     H     CH.sub.3                                                                             198- 199                             4                                                                                    ##STR32##         O     H     CF.sub.3                                                                             222- 223                             5                                                                                    ##STR33##         O     Cl    Cl    134- 135                             6                                                                                    ##STR34##         O     Cl    Cl    205- 206                             7                                                                                    ##STR35##         O     CH.sub.3                                                                             CH.sub.3                                                                             202- 203                             8                                                                                    ##STR36##         O     Cl    Cl    258- 263                             9                                                                                    ##STR37##         O     Cl    Cl    253- 255                             10                                                                                   ##STR38##         O     Cl    Cl    207- 208                             11                                                                                   ##STR39##         O     Cl    Cl                                         12                                                                                   ##STR40##         O     CH.sub.3                                                                             Cl                                         13                                                                                   ##STR41##         O     Br    Cl                                         14                                                                                   ##STR42##         O     CF.sub.3                                                                             CF.sub.3                                   15                                                                                   ##STR43##         O     OCH.sub.3                                                                            OCH.sub.3                                  16                                                                                   ##STR44##         S     Cl    Cl                                         17                                                                                   ##STR45##         S     CH.sub.3                                                                             CH.sub.3                                   18                                                                                   ##STR46##         O     Cl    Cl                                         19                                                                                   ##STR47##         S     Br    Br                                         20                                                                                   ##STR48##         O     CH.sub.3                                                                             OCH.sub.3                                  21                                                                                   ##STR49##         S     OCH.sub.3                                                                            OCH.sub.3                                  22                                                                                   ##STR50##         S     CF.sub.3                                                                             CF.sub.3                                   23                                                                                   ##STR51##         O     Cl    Cl                                         24                                                                                   ##STR52##         O     CF.sub.3                                                                             CF.sub.3                                   25                                                                                   ##STR53##         O     CH.sub.3                                                                             CH.sub.3                                   26                                                                                   ##STR54##         O     OCH.sub.3                                                                            OCH.sub.3                                  27                                                                                   ##STR55##         S     CH.sub.3                                                                             OCH.sub.3                                  28                                                                                   ##STR56##         S     Cl    Cl                                         29                                                                                   ##STR57##         O     Cl    Cl                                         30                                                                                   ##STR58##         O     CH.sub.3                                                                             Cl                                         31                                                                                   ##STR59##         O     CF.sub.3                                                                             Cl                                         32                                                                                   ##STR60##         S     OCH.sub.3                                                                            OCH.sub.3                                  33                                                                                   ##STR61##         S     CF.sub.3                                                                             CF.sub.3                                   34                                                                                   ##STR62##         O     Cl    Cl                                         35                                                                                   ##STR63##         O     Br    Br                                         36                                                                                   ##STR64##         S     CF.sub.3                                                                             CF.sub.3                                   37                                                                                   ##STR65##         S     Cl    Cl                                         38                                                                                   ##STR66##         O     Cl    Cl                                         39                                                                                   ##STR67##         O     Cl    Cl                                         40                                                                                   ##STR68##         S     Cl    Br                                         41                                                                                   ##STR69##         S     CH.sub.3                                                                             CH.sub.3                                   42                                                                                   ##STR70##         O     CH.sub.3                                                                             Cl                                         43                                                                                   ##STR71##         O     OCH.sub.3                                                                            OCH.sub.3                                  44                                                                                   ##STR72##         O     CF.sub.3                                                                             CF.sub.3                                   45                                                                                   ##STR73##         O     Br    Br                                         46                                                                                   ##STR74##         O     CH.sub.3                                                                             CH.sub. 3                                  47                                                                                   ##STR75##         O     CF.sub.3                                                                             CF.sub.3                                   48                                                                                   ##STR76##         O     OCH.sub.3                                                                            OCH.sub.3                                  49                                                                                   ##STR77##         S     Cl    Cl                                         50                                                                                   ##STR78##         S     Cl    Br                                         ______________________________________                                    

EXAMPLE 3 cis-4-Methylcyclohexane-5'-spiro-3'-(3,5-dibromophenyl)hydantoin STEP A: cis-4-methylcyclohexane-5'-spiro-3'-(2-nitrophenyl)-hydantoin

18.2 g (0.1 mol) of cis-4-methylcyclohexane-5'-spiro-hydantoin, 18 g (0.1 mol) of 2-nitro-chlorobenzene and 41.4 g (0.3 mol) of potassium carbonate were dissolved or suspended in 100 ml of dimethylformamide and the mixture was then stirred for 5 hours at about 120° C. The mixture was then poured onto ice and the precipitate formed was vacuum filtered, washed thoroughly with water and crystallized from acetonitrile to obtain 15.5 g (51% of theory) of title compound melting at 227°-229° C.

STEP B: cis-4-methylcyclohexane-5'-spiro-3'-(2-aminophenyl)hydantoin

15.2 g (0.05 mol) of cis-4-methylcyclohexane-5'-spiro-3'-(2-nitrophenyl)-hydantoin were dissolved in 200 ml of methanol and 5 ml of conc. hydrochloric acid and, after the addition of 4 g of catalyst (Pd/C, 10%), the mixture was hydrogenated at a maximum temperature of 40° C. and under a pressure of 5 bar. After hydrogen absorption ceased, the catalyst was removed by vacuum filtration and the mother liquor was concentrated by evaporation. The residue was taken up in water and the solution was neutralized with sodium bicarbonate. The solid product obtained was vacuum filtered, washed with water and crystallized from isopropanol to obtain 11.5 g (84% of theory) of the title compound melting at 255°-256° C.

STEP C: cis-4-Methylcyclohexane-5'-spiro-3'-(2-amino-3,5-dibromophenyl)hydantoin

27.33 g (0.1 mol) of cis-4-methyl-cyclohexane-5'-spiro-3'-(2-amino-phenyl)hydantoin were dissolved in 200 ml of glacial acetic acid and a solution of 32 g (0.2 mol) of bromine in 50 ml of glacial acetic acid was added thereto dropwise over 30 minutes at ambient temperature. The resulting mixture was stirred for about 30 minutes, then was diluted with 1 liter of water and the precipitate was vacuum filtered. The product was washed with water and crystallized from acetonitrile to obtain 35.4 g (82% of theory) of the title compound melting at 264°-266° C.

STEP D: cis-4-Methylcyclohexane-5'-spiro-3'-(3,5-dibromophenyl)-hydantoin

21.6 g (0.05 mol) of cis-4-methyl-5'-spiro-3'-(2-amino-3,5-dibromophenyl)-hydantoin were dissolved in 300 ml of ethanol and 10 ml of conc. sulfuric acid and the mixture was heated to reflux. Then, 3.8 g (0.055 mol) of sodium nitrite were added thereto in batches over about 20 minutes and the resulting mixture was refluxed for 1 hour with stirring. After it had cooled, it was diluted with 1 liter of ice water and the resulting precipitate was vacuum filtered, washed with water and crystallized from acetonitrile to obtain 12.3 g (59% of theory) of the title compound melting at 247°-249° C.

EXAMPLE 4 cis-2-Ethylcyclohexane-5'-spiro-3'-(3,5-dibromophenyl)-hydantoin (a) cis-2-ethylcyclohexane-4'-spiro-3'-(2,4-dinitrophenyl)-hydantoin

39 g (0.2 mol) of cis-2-ethylcyclohexane-5'-spiro-hydantoin, 40.4 g (0.2 mol) of 1-chloro-2,4-dinitrobenzene, 83 g (0.6 mol) of potassium carbonate and 1 g of tetrabutylammonium hydrogen sulfate were stirred into 200 ml of dimethylsulfoxide at 10° C. for 6 hours and the mixture was then diluted with 500 ml of water. The mixture was vacuum filtered, and the product was washed with water and cold methanol and dried to obtain 62.4 g (86% of theory) of title compound melting at 231°-232° C.

(b) cis-2-ethylcyclohexane-5'-spiro-3'-(2,4-diaminophenyl)-hydantoin

36.2 g (0.1 mol) of cis-2-ethylcyclohexane-5'-spiro-3'-(2,4-dinitrophenyl)-hydantoin were dissolved in 500 ml of methanol and 20 ml of conc. hydrochloric acid and after 10 g of catalyst (10% Pd/C) were added thereto, the mixture was hydrogenated at a temperature of not more than 65° C. under a pressure of 5 bar. Then the catalyst was removed by vacuum filtering and the filtrate was concentrated by evaporation. The residue was taken up in water and the solution was neutralized with sodium bicarbonate. The precipitate formed was vacuum filtered, washed with water and crystallized from isopropanol to obtain 25.4 g (84% of theory) of title compound melting at 183°-185° C.

(c) cis-2-Ethylcyclohexane-5'-spiro-4'-(2,4-diamino-3,5-dibromophenyl)-hydantoin

15 g (0.05 mol) of cis-2-ethylcyclohexane-5'-spiro-3'-(2,4-diaminophenyl)-hydantoin were dissolved in 100 ml of glacial acetic acid and a solution of 5.06 g (0.1 mol) of bromine in 20 ml of glacial acetic acid was added dropwise thereto at ambient temperature over 10 minutes. The resulting mixture was stirred for another 20 minutes, then 300 ml of ice water were added. The solid matter was separated by vacuum filtration and was washed thoroughly with water and dried in vacuo to obtain 18 g (78.3% of theory) of title compound melting at 263°-265° C.

(d) cis-2-Ethylcyclohexane-5'-spiro-3'-(3,5-dibromophenyl)-hydantoin

A solution of 3.5 g (0.03 mol) of isoamyl nitrite in 50 ml of dimethylformamide was heated to 55° C. and at this temperature, a solution of 6.9 g (0.015 mol) of cis-2-ethyl-cyclohexane-5'-spiro-3'-(2,4-diamino-3,5-dibromopenyl)-hydantoin in 20 ml of dimethylformamide was added dropwise thereto over 1 hour. The temperature was then raised to 70°-80° C. until the development of nitrogen gas ceased. The mixture was then concentrated by evaporation in vacuo and the dark residue was purified by column chromatography (silica gel/ethyl acetate) to obtain 3.9 g (59% of theory) of title compound melting at 213°-215° C.

Using the procedure of Examples 3 and 4, the compounds of Table II were prepared by selection of the appropriate starting materials.

                  TABLE II                                                         ______________________________________                                         No.  A              W      X      Y     Mp °C.                          ______________________________________                                               ##STR79##     O      Br     CH.sub.3                                                                             193-195                                2                                                                                    ##STR80##     O      Cl     CH.sub.3                                                                             202-203                                3                                                                                    ##STR81##     O      Cl     Cl    193-195                                4                                                                                    ##STR82##     O      Cl     Cl    212-213                                5                                                                                    ##STR83##     O      CH.sub.3                                                                              CH.sub.3                                                                             162-163                                6                                                                                    ##STR84##     O      CH.sub.3                                                                              CH.sub.3                                                                             208-211                                7                                                                                    ##STR85##     O      Cl     Cl    188-189                                8                                                                                    ##STR86##     O      OCH.sub.3                                                                             OCH.sub.3                                                                            177-179                                9                                                                                    ##STR87##     O      CF.sub.3                                                                              CF.sub.3                                                                             179-181                                ______________________________________                                    

EXAMPLE 5 cis-2-Methylcyclohexane-5'-spiro-3'-(2,6-dichloropyridyl-4)-hydantoin

192 g (1 mol) of cis-2-methylcyclohexane-5'-spiro-hydantoin, 194 g (1 mol) of 2,6-dichloro-4-nitropyridine, 207 g (1.5 mol) of potassium carbonate and 3.4 g (0.01 mol) of tetrabutylammonium hydrogen sulfate were dissolved or suspended in 1000 ml of dimethylsulfoxide at ambient temperature and the mixture was then stirred at 15°-20° C. for another 16 hours. Then, about 5000 ml of ice water were introduced and the precipitate formed was vacuum filtered, washed thoroughly with water and recrystallized from acetonitrile to obtain 250 g (79% of theory) of title compound melting at 227°-229° C.

Using the procedure of Example 5, the compounds listed in Table III were prepared by selection of the appropriate starting materials.

                  TABLE III                                                        ______________________________________                                         No.   A                   X      Y   Mp °C.                             ______________________________________                                                ##STR88##          Cl     Cl  216-218                                   2                                                                                     ##STR89##          Cl     Cl  190-191                                   3                                                                                     ##STR90##          Cl     Cl  138-140                                   4                                                                                     ##STR91##          Cl     Cl  191-193                                   5                                                                                     ##STR92##          Cl     Cl  125-127                                   6                                                                                     ##STR93##          Cl     Cl  238-242                                   ______________________________________                                    

EXAMPLE 6 5-Methyl-5-cyclopropyl-3-[4-(2,6-dichloropyridyl)]-hydantoin

A suspension consisting of 3.1 g of 5-methyl-5-cyclopropyl-hydantoin, 3.86 g of 2,6-dichloro-4-nitropyridine and 5.6 g of potassium carbonate in 10 ml of dimethylformamide was stirred for 18 hours at 20° C. and then was added to 100 ml of water. After 30 minutes of stirring, the resulting precipitate was vacuum filtered and taken up in methylene chloride. After drying and removal of the solvent, 3.2 g (64% of theory) of 5-methyl-5-cyclopropyl-3-[4-(2,6-dichloropyridyl)]-hydantoin melting at 160° C. (reprecipitated from toluene/petroleum ether) were obtained.

EXAMPLE 7 5-Methyl-5-cyclopropyl-3-(3,5-dimethylphenyl)-hydantoin

0.3 g of triethylamine were added to a solution of 0.8 g of methyl 1-(3,5-dimethylphenyl)-3-[2-(2-cyclopropyl)propanoate]-urea in 30 ml of methanol and the mixture was refluxed for 12 hours. After the solvent had been removed, the residue was triturated with petroleum ether and the crystalline precipitate obtained was vacuum filtered to obtain 0.6 g (85% of theory) of title compound melting at 121° C.

EXAMPLE 8 5-n-Propyl-5-(1-methylethyl)-3-(3,5-dichlorophenyl)-2-thio-hydantoin

A solution of 2.0 g of 3,5-dichlorophenyl isothiocyanate in 10 ml of absolute tetrahydrofuran was added dropwise at 20° C. to a solution of 1.7 g of methyl 2-amino-2-(1-methylethyl)-pentanoate in 10 ml of absolute tetrahydrofuran and the mixture was stirred at 20° C. for a further 4 hours. Then the solvent was removed and the residue was recyrstallized from diisopropyl ether to obtain 1.6 g (46% of theory) of title compound melting at 160° C.

Using the procedure of Example 7 and 8, the compounds of Table IV were prepared by selection of the appropriate starting materials.

                                      TABLE IV                                     __________________________________________________________________________      ##STR94##                                                                     No.                                                                               Q  W  X   Y   R.sub.4   R.sub.5      Mp [°C.]                        __________________________________________________________________________      1 N  O  Cl  Cl  CH.sub.3  i-C.sub.3 H.sub.7                                                                           129                                     2 N  O  Cl  Cl  i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                           157-159                                 3 N  O  Cl  Cl  CH.sub.3  t-C.sub.4 H.sub.9                                                                           167-170                                 4 N  O  Cl  Cl  n-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                           91-93                                   5 N  O  Cl  Cl  CH.sub.3  CH.sub.2CH.sub.2CHCH.sub.2                                                                  76-81                                   6 N  O  Cl  Cl  C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                                                            97-103                                 7 N  O  Cl  Cl  C.sub.6 H.sub.5                                                                          C.sub.6 H.sub.5                                                                             190-194                                 8 N  O  Cl  Cl  CH.sub.3  C.sub.6 H.sub.5                                                                             167-170                                 9 N  O  Cl  Cl  CH.sub.3  n-C.sub.4 H.sub.9                                   10 N  O  Cl  Cl  CH.sub. 3                                                                                 ##STR95##   161-163                                11 N  O  Cl  Cl  CH.sub.3  C.sub.2 H.sub.5                                     12 N  O  Cl  Cl  CH.sub.3  i-C.sub.4 H.sub.9                                                                           133-138                                13 N  O  Cl  Cl  CH.sub.3  s-C.sub.4 H.sub.9                                                                           105-112                                14 N  O  Cl  Cl  C.sub.2 H.sub.5                                                                          t-C.sub.4 H.sub.9                                   15 CH O  Cl  Cl  CH.sub.3  CH.sub.3     159-161                                16 CH O  Cl  Cl  CH.sub.3  i-C.sub.3 H.sub.7                                                                           124                                    17 CH S  Cl  Cl  CH.sub.3  i-C.sub.3 H.sub.7                                                                           168                                    18 CH O  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3  i-C.sub.3 H.sub.7                                                                           134-136                                19 CH S  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3  i-C.sub.3 H.sub.7                                                                           150                                    20 CH O  Cl  Cl  CH.sub.3                                                                                  ##STR96##   145                                    21 CH S  Cl  Cl  CH.sub.3                                                                                  ##STR97##   121                                    22 CH S  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                                  ##STR98##   175                                    23 CH O  Cl  Cl  CH.sub.3  t-C.sub.4 H.sub.9                                                                           230                                    24 CH O  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3  t-C.sub.4 H.sub.9                                                                           153                                    25 CH S  Cl  Cl  CH.sub.3  t-C.sub.4 H.sub.9                                                                           207                                    26 CH O  Cl  Cl  n-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                           140-145                                27 CH O  CH.sub.3                                                                           CH.sub.3                                                                           n-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                           110                                    28 CH O  Cl  Cl  CH.sub.3  CH.sub.2CH.sub.2CHCH.sub.2                                                                   80                                    29 CH O  Cl  Cl  CH.sub.3  n-C.sub.4 H.sub.9                                                                           100                                    30 CH O  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3  n-C.sub.4 H.sub.9                                                                           122                                    31 CH O  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3  CH.sub.2CH.sub.2CHCH.sub.2                                                                   90                                    32 CH S  Cl  Cl  CH.sub.3  CH.sub.2CH.sub.2CHCH.sub.2                                                                  157                                    33 CH S  Cl  Cl  CH.sub.3  n-C.sub.4 H.sub.9                                                                           168                                    34 CH O  Cl  Cl  CH.sub.3  C.sub.6 H.sub.5                                                                             158                                    35 CH O  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3  C.sub.6 H.sub.5                                                                             168                                    36 CH O  Cl  Cl  C.sub.6 H.sub.5                                                                          C.sub.6 H.sub.5                                                                             136                                    37 CH O  CH.sub.3                                                                           CH.sub.3                                                                           C.sub.6 H.sub.5                                                                          C.sub.6 H.sub.5                                     38 CH S  Cl  Cl  CH.sub.3  C.sub.6 H.sub.5                                                                             190                                    39 CH S  Cl  Cl  C.sub.6 H.sub.5                                                                          C.sub.6 H.sub.5                                     40 CH O  Cl  Cl  CH.sub.3                                                                                  ##STR99##   205                                    41 CH O  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                                  ##STR100##                                         42 CH S  Cl  Cl  CH.sub.3                                                                                  ##STR101##                                         43 CH O  Cl  Cl  i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                           210                                    44 CH O  CH.sub.3                                                                           CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                   45 CH S  Cl  Cl  i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                           amorphous                              46 CH O  Cl  Cl  CH.sub.3  C.sub.2 H.sub.5                                     47 CH O  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3  C.sub.2 H.sub.5                                     48 CH S  Cl  Cl  CH.sub.3  C.sub.2 H.sub.5                                     49 CH O  Cl  Cl  CH.sub.3  i-C.sub.4 H.sub.9                                   50 CH O  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3  i-C.sub.4 H.sub.9                                   51 CH S  Cl  Cl  CH.sub.3  i-C.sub.4 H.sub.9                                                                           144                                    52 CH O  Cl  Cl  C.sub.2 H.sub. 5                                                                         i-C.sub.3 H.sub.7                                   53 CH O  CH.sub.3                                                                           CH.sub.3                                                                           C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                   54 CH S  Cl  Cl  C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                   55 CH O  Cl  Cl  CH.sub.3  s-C.sub.4 H.sub.9                                                                           130                                    56 CH O  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3  s-C.sub.4 H.sub.9                                   57 CH S  Cl  Cl  CH.sub.3  s-C.sub.4 H.sub.9                                                                           142                                    58 CH O  Cl  Cl  C.sub.2 H.sub.5                                                                          t-C.sub.4 H.sub.9                                   59 CH O  CF.sub.3                                                                           CF.sub.3                                                                           CH.sub.3  i-C.sub.3 H.sub.7                                                                           124                                    60 CH O  OCH.sub.3                                                                          OCH.sub.3                                                                          CH.sub.3  i-C.sub.3 H.sub.7                                                                           129-130                                61 CH O  Br  Br  CH.sub.3  i-C.sub.3 H.sub.7                                                                           140                                    62 CH O  Cl  CH.sub.3                                                                           CH.sub.3  i-C.sub.3 H.sub.7                                                                           120                                    63 CH O  Br  CH.sub.3                                                                           CH.sub.3  i-C.sub.3 H.sub.7                                                                           135                                    64 CH S  OCH.sub.3                                                                          Cl  CH.sub.3  i-C.sub.3 H.sub.7                                   65 CH O  Cl  Br  C.sub.2 H.sub.5                                                                           ##STR102##                                         66 N  S  Cl  CH.sub.3                                                                           C.sub.2 H.sub.5                                                                          t-C.sub.4 H.sub.9                                   67 N  O  OCH.sub.3                                                                          Cl  i-C.sub. 3 H.sub.7                                                                       i-C.sub.3 H.sub.7                                   68 CH O  CF.sub.3                                                                           Cl  CH.sub.3                                                                                  ##STR103##                                         69 CH S  Cl  CH.sub.3                                                                           CH.sub.3  i-C.sub.3 H.sub.7                                   70 N  S  Cl  CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                   71 CH S  Cl  Cl                                                                                  ##STR104##                                                                              C.sub.6 H.sub.5                                                                             146                                    72 CH S  Cl  Cl  CH.sub.3  CH.sub.2OCH.sub.3                                                                           164                                    73 CH O  Cl  Cl  CH.sub.3  CH.sub.2OCH.sub.3                                                                           134                                    74 CH O  Cl  Cl  CH.sub.3                                                                                  ##STR105##  185                                    75 CH O  Cl  Cl  C.sub.2 H.sub.5                                                                          i-C.sub.4 H.sub.9                                                                           140                                    76 CH O  Cl  Cl  CH.sub.3  CH.sub.2C.sub.6 H.sub.5                                                                     142                                    77 N  O  Cl  Cl  C.sub.6 H.sub.5                                                                           ##STR106##  137-140                                78 N  O  Cl  Cl                                                                                  ##STR107##            228-233                                79 N  O  Cl  Cl  CH.sub.3  CHOCH.sub.3  156-158                                80 N  O  Cl  Cl  CH.sub.3                                                                                  ##STR108##  148-155                                81 N  O  Cl  Cl                                                                                  ##STR109##                                                                               ##STR110##  195-199                                82 N  O  Cl  Cl  CH.sub.3  CH.sub.2OC.sub.6 H.sub.5                                                                    128-135                                __________________________________________________________________________

Starting or intermediate products for the compounds of Table IV.

                  TABLE V                                                          ______________________________________                                         Hydantoins of formula                                                           ##STR111##                                                                    No.   R.sub.4          R.sub.5    Mp [°C.]                              ______________________________________                                         1     i-C.sub.3 H.sub.7                                                                               CH.sub.3   176-177                                      2     t-C.sub.4 H.sub.9                                                                               CH.sub.3   220                                                 ##STR112##      CH.sub.3   149-150                                      4     CH.sub.2CHCH.sub.2CH.sub.2                                                                      CH.sub.3   117                                          5     n-C.sub.3 H.sub.7                                                                               i-C.sub.3 H.sub.7                                                                         188                                          6     i-C.sub.3 H.sub.7                                                                               i-C.sub.3 H.sub.7                                                                         210-212                                      7     n-C.sub.4 H.sub.9                                                                               CH.sub.3   105-106                                      8     C.sub.6 H.sub.5  CH.sub.3   200                                          9     C.sub.6 H.sub.5  C.sub.6 H.sub.5                                                                           300                                          10    C.sub.3 H.sub.7  CH.sub.3   124-126                                      11    i-C.sub.4 H.sub.9                                                                               CH.sub.3   147                                          12    i-C.sub.3 H.sub.7                                                                               C.sub.2 H.sub.5                                         13    t-C.sub.4 H.sub.9                                                                               C.sub.2 H.sub.5                                         14    s-C.sub.4 H.sub.9                                                                               CH.sub.3   179-189                                      15                                                                                    ##STR113##      CH.sub.3   158                                          16                                                                                    ##STR114##                                                                                      ##STR115##                                                                               199-200                                      17    CH.sub.2OCH.sub.3                                                                               CH.sub.3   170-173                                      18                                                                                    ##STR116##      C.sub.6 H.sub.5                                                                           214                                          19    CH.sub.3                                                                                         ##STR117##                                                                               226-228                                      20    C.sub.6 H.sub.5                                                                                  ##STR118##                                                                               >250                                         ______________________________________                                    

                  TABLE VI                                                         ______________________________________                                         Aminocarboxylic acid hydrochlorides of the formula                              ##STR119##                                                                    No.  R.sub.4          R.sub.5    Mp. [°C.]                              ______________________________________                                         1    t-C.sub.4 H.sub.9                                                                               CH.sub.3   250                                           2    i-C.sub.3 H.sub.7                                                                               CH.sub.3   250                                                 ##STR120##      CH.sub.3   ca. 255                                       4    CH.sub.2CHCH.sub.2CH.sub.2                                                                      CH.sub.3   250                                           5    CH.sub.3CH.sub.2CH.sub.2                                                                        i-C.sub.3 H.sub.7                                                                         ca. 230                                       6    i-C.sub.3 H.sub.7                                                                               i-C.sub.3 H.sub.7                                        7    n-C.sub.4 H.sub.9                                                                               CH.sub.3   230                                           8    C.sub.6 H.sub.5  CH.sub.3   >250                                          9    C.sub.6 H.sub.5  C.sub.6 H.sub.5                                                                           >250                                          10                                                                                   ##STR121##      CH.sub.3   amorphous                                     11   C.sub.3 H.sub.7  CH.sub.3   215                                           12   i-C.sub.4 H.sub.9                                                                               CH.sub.3                                                 13   i-C.sub.4 H.sub.7                                                                               C.sub.2 H.sub.5                                          14   t-C.sub.4 H.sub.9                                                                               C.sub.2 H.sub.5                                          15   s-C.sub.4 H.sub.9                                                                               CH.sub.3                                                 16                                                                                   ##STR122##      C.sub. 6 H.sub.5                                                                          240                                           17   CH.sub.3                                                                                         ##STR123##                                                                               >220                                          18                                                                                   ##STR124##                                                                                      ##STR125##                                                                               >250                                          ______________________________________                                    

                                      TABLE VII                                    __________________________________________________________________________     Aminocarboxylic acid derivatives                                                ##STR126##                                                                                                 Physical data                                     No. R.sub.4     R.sub.5                                                                            Z        mp [°C.]                                   __________________________________________________________________________     1   i-C.sub.3 H.sub.7                                                                          CH.sub.3                                                                           CH.sub.3 Bp. 69-70° C./                                                          21 mbar                                           2   t-C.sub.4 H.sub.9                                                                          CH.sub.3                                                                           CH.sub.3                                                   3               CH.sub.3                                                                           CH.sub.3                                                   4   CH.sub.2CHCH.sub.2CH.sub.2                                                                 CH.sub.3                                                                           CH.sub.3                                                   5   n-C.sub.3 H.sub.7                                                                          i-C.sub.3 H.sub.7                                                                  CH.sub.3                                                   6   n-C.sub.4 H.sub.9                                                                          CH.sub.3                                                                           C.sub.2 H.sub.5                                            7   C.sub.6 H.sub.5                                                                            CH.sub.3                                                                           CH.sub.3                                                   8   C.sub.6 H.sub.5                                                                            C.sub.6 H.sub.5                                                                    CH.sub.3                                                        ##STR127## CH.sub.3                                                                           CH.sub.3                                                   10  i-C.sub.3 H.sub.7                                                                          CH.sub.3                                                                           C.sub.2 H.sub.5                                            11  i-C.sub.3 H.sub.7                                                                          CH.sub.3                                                                           i-C.sub.3 H.sub.7                                          12  i-C.sub.3 H.sub.7                                                                          CH.sub.3                                                                           CH.sub.2CHCH.sub.2                                         13  i-C.sub.3 H.sub.7                                                                          CH.sub.3                                                                           C.sub.6 H.sub.5                                            14  C.sub.2 H.sub.5                                                                            CH.sub.3                                                                           CH.sub.3                                                   15  i-C.sub.4 H.sub.9                                                                          CH.sub.3                                                                           CH.sub.3                                                   16  i-C.sub.3 H.sub.7                                                                          C.sub.2 H.sub.5                                                                    CH.sub.3                                                   17  s-C.sub.4 H.sub.9                                                                          CH.sub.3                                                                           CH.sub.3                                                   18  t-C.sub.4 H.sub.9                                                                          C.sub.2 H.sub.5                                                                    CH.sub.3                                                   19  CH.sub.3    i-C.sub.3 H.sub.7                                                                  n-C.sub.4 H.sub.8OCH.sub.3                                 20  CH.sub.3    i-C.sub.3 H.sub.7                                                                  C.sub.2 H.sub.4OC.sub.2 H.sub.5                            __________________________________________________________________________

The compounds in the above Table were characterised by NMR and IR spectra.

                                      TABLE VIII                                   __________________________________________________________________________     Compounds of the formula                                                        ##STR128##                                                                    No.                                                                               X   Y   R.sub.4                                                                            R.sub.5     Z        Mp [°C.]                            __________________________________________________________________________     1  Cl  Cl  CH.sub.3                                                                           CH.sub.3    C.sub.2 H.sub.5                                                                         172                                        2  Cl  Cl  CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          CH.sub.3 178                                        3  Cl  Cl  CH.sub.3                                                                            ##STR129## CH.sub.3 168                                        4  Cl  Cl  CH.sub.3                                                                           t-C.sub.4 H.sub.9                                                                          CH.sub.3 194                                        5  Cl  Cl  n-C.sub.3 H.sub.7                                                                  i-C.sub.3 H.sub.7                                                                          CH.sub.3 145                                        6  Cl  Cl  CH.sub.3                                                                           CH.sub.2CHCH.sub.2CH.sub.2                                                                 H        amorphous                                  7  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          CH.sub.3 182                                        8  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                            ##STR130## CH.sub.3 161                                        9  CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                           t-C.sub.4 H.sub.9                                                                          CH.sub.3 206                                        10 Cl  Cl  CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          C.sub.2 H.sub.5                                                                         155-158                                    11 Cl  Cl  CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          i-C.sub.3 H.sub.7                                                                       85-90                                      12 Cl  Cl  CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          CH.sub.2CHCH.sub.2                                                                      144                                        13 Cl  Cl  CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          C.sub.6 H.sub.5                                     14 Cl  Cl  CH.sub.3                                                                           n-C.sub.4 H.sub.9                                                                          C.sub.2 H.sub.5                                                                         138-140                                    15 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                           n-C.sub.4 H.sub.9                                                                          C.sub.2 H.sub.5                                                                         134                                        16 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2CHCH.sub.2CH.sub.2                                                                 H                                                   17 Cl  Cl  CH.sub.3                                                                           C.sub.6 H.sub.5                                                                            C.sub.2 H.sub.5                                                                         180                                        18 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                           C.sub.6 H.sub.5                                                                            C.sub.2 H.sub.5                                                                         185                                        19 Cl  Cl  C.sub.6 H.sub.5                                                                    C.sub.6 H.sub.5                                                                            C.sub.2 H.sub.5                                                                         200                                        20 CH.sub.3                                                                           CH.sub.3                                                                           C.sub.6 H.sub.5                                                                    C.sub.6 H.sub.5                                                                            CH.sub.3                                            21 Cl  Cl  CH.sub.3                                                                            ##STR131## C.sub.2 H.sub.5                                                                         223                                        22 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                            ##STR132## H        205                                        23 Cl  Cl  i-C.sub.3 H.sub.7                                                                  i-C.sub.3 H.sub.7                                                                          H        75-80                                      24 CH.sub.3                                                                           CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                  C.sub.3 H.sub.7                                                                            H                                                   25 Cl  Cl  CH.sub.3                                                                           C.sub.2 H.sub.5                                                                            CH.sub.3                                            26 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                           C.sub.2 H.sub.5                                                                            CH.sub.3                                            27 Cl  Cl  CH.sub.3                                                                           i-C.sub.4 H.sub.9                                                                          CH.sub.3                                            28 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                           i-C.sub.4 H.sub.9                                                                          CH.sub.3                                            29 Cl  Cl  C.sub.2 H.sub.5                                                                    i-C.sub.3 H.sub.7                                                                          CH.sub.3 185                                        30 CH.sub.3                                                                           CH.sub.3                                                                           C.sub.2 H.sub.5                                                                    i-C.sub.3 H.sub.7                                                                          CH.sub.3                                            31 Cl  Cl  CH.sub.3                                                                           s-C.sub.4 H.sub.9                                                                          CH.sub.3 174-176                                    32 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                           s-C.sub.4 H.sub.9                                                                          CH.sub.3                                            33 Cl  Cl  C.sub.2 H.sub.5                                                                    t-C.sub.4 H.sub.9                                                                          CH.sub.3                                            34 CF.sub.3                                                                           CF.sub.3                                                                           CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          C.sub.2 H.sub.5                                                                         160                                        35 OCH.sub.3                                                                          OCH.sub.3                                                                          CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          C.sub.2 H.sub.5                                                                         160                                        36 Br  Br  CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          C.sub.2 H.sub.5                                                                         190                                        37 CH.sub.3                                                                           Cl  CH.sub.3                                                                            ##STR133## C.sub.2 H.sub.4OCH.sub.3                            38 CH.sub.3                                                                           Cl  CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          n-C.sub.4 H.sub.9                                   39 Cl  OCH.sub.3                                                                          CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          n-C.sub.4 H.sub.8OCH.sub.3                          40 Cl  CF.sub.3                                                                           CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          C.sub.2 H.sub.4OC.sub.2 H.sub.5                     41 Cl  CH.sub.3                                                                           CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          C.sub.2 H.sub.5                                                                         165                                        42 Br  CH.sub.3                                                                           CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          C.sub.2 H.sub.5                                                                         172                                        43 CH.sub.3                                                                           CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                  n-C.sub.4 H.sub.9                                                                          CH.sub.3 123                                        44 Cl  Cl  CH.sub.3                                                                           CH.sub.2OCH.sub.3                                                                          CH.sub.3 145-148                                    45 Cl  Cl  CH.sub.3                                                                            ##STR134## CH.sub.3 200-205                                    46 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2CH.sub.2CHCH.sub.2                                                                 C.sub.2 H.sub.5                                                                         130                                        47 Cl  Cl  CH.sub.3                                                                           CH.sub.2CH.sub.2CHCH.sub.2                                                                 C.sub.2 H.sub.5                                                                         140                                        48 Cl  Cl  C.sub.2 H.sub.5                                                                    t-C.sub.4 H.sub.9                                                                          C.sub.2 H.sub.5                                                                         140                                        49 Cl  Cl  CH.sub.3                                                                           CH.sub.2C.sub.6 H.sub.5                                                                    C.sub.2 H.sub.5                                                                         180                                        50 Cl  Cl  CH.sub.3                                                                            ##STR135## H        167                                        51 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                            ##STR136## H        159                                        52 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          H        185                                        53 Cl  Cl  CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          H        188                                        54 CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                           i-C.sub.3 H.sub.7                                                                          C.sub.2 H.sub.5                                                                         145-147                                    __________________________________________________________________________

FORMULATION EXAMPLES

A: Suspension powder

25% by weight of a compound of formula I

55% by weight of kaolin

10% by weight of colloidal silicic acid

9% by weight of lignin sulfonate

1% by weight of sodium tetrapropylene benzenesulfonate

B: Suspension powder

80% by weight of a compound of formula I

8% by weight of calcium lignin sulfonate

5% by weight of colloidal silicic acid

5% by weight of sodium sulfate

2% by weight of sodium diisobutylnaphthalenesulfonate.

HERBICIDAL TEST DATA

The herbicidal activity and compatibility of the compounds of the invention were tested in greenhouse tests and the results were evaluated on a ten-point scale, where 1=100% activity and 10=no activity. Plants I to III were weeds, while IV to VI were useful plants.

    ______________________________________                                                 Quantity                                                               Active  applied in                                                             substance                                                                              kg/ha       I     II    III IV    V   VI                               ______________________________________                                         Example 1                                                                              1           1     1     1   10    10  10                                       0.5         2     1     1   10    10  10                               Table I 1           1     1     1   --    10  10                               No. 6   0.5         1     1     1   --    10  10                               ______________________________________                                    

I: Echinocloa crus-galli

II: Cynodon dactylon

III: Digitaria sanguinalis

IV: Oryza sativa

V: Gossypium hirsutum

VI: Glyzine max.

As the Table shows, the active compounds of the invention combine a very good activity (predominantly 1 on the assessment scale) with excellent compatibility (10 on the assessment scale in every case) with the useful plants.

Various modifications of the compounds and methods of the invention may be made without departing from the spirit or scope thereof and it is to be understood that the invention is intentended to be limited only as defined in the appended claims. 

What we claim is:
 1. A compound of the formula ##STR137## wherein Q is --CH═ or --N═; ##STR138## R₁, R₂ and R₃ are each independently hydrogen or alkyl of 1 to 4 carbon atoms, at least one of R₁, R₂ and R₃ being hydrogen; R₄ and R₅ are each independently alkyl of 1 to 4 carbon atoms or cycloalkyl of 3 to 6 carbon atoms; provided that at least one of them is C₃ -alkyl or C₃ -cycloalkyl; and X and Y are halogen, with the proviso that Q is not --CH═ when A is ##STR139##
 2. A compound of claim 1 wherein X is chlorine or bromine, and Y is chlorine or bromine.
 3. The compound of claim 1 which is cyclohexane-5'-spiro-3'-(3,5-dichlorophenyl)-hydantoin.
 4. A compound of claim 1, where A is ##STR140##
 5. A compound of claim 1, where A is ##STR141##
 6. The compound of claim 1 which is 5',5'-diisopropyl-3-[4-(2,6-dichloropyridyl)]-hydantoin.
 7. An herbicidal composition comprising an herbicidally effective amount of at least one compound of claim 1 and an inert carrier.
 8. A composition of claim 7 wherein X is chlorine or bromine, and Y is chlorine or bromine.
 9. A composition of claim 7 wherein the active compound is 2-methyl-cyclohexane-5'-spiro-3'-(3,5-dichlorophenyl)-hydantoin.
 10. A herbicidal composition of claim 7 wherein the active compound is 5',5'-diisopropyl-3-[4-(2,6-dichloropyridyl)]-hydantoin.
 11. The method of selectively combatting weeds and wild grass comprising contacting weeds and wild grass with an herbicidally effective amount of at least one compound of claim
 1. 12. The method of claim 11 wherein X is chlorine or bromine, and Y is chlorine or bromine.
 13. The method of claim 11 wherein the active compound is 2-methyl-cyclohexane-5'-spiro-3'-(3,5-dichlorophenyl)-hydantoin. 